聚磷腈材料在航空航天及军工领域的应用研究

简要介绍了聚磷腈的结构和性能,概述了六氯环三磷腈、聚二氯磷腈和聚磷腈的合成方法,综述了其在航空航天及军工领域的应用,包括在耐高温阻燃涂层、阻燃泡沫橡胶、火箭发动机绝热层、密封材料等领域的应用,并指出了我国聚磷腈材料发展存在的问题,最后对聚磷腈的发展前景进行了展望。     

聚磷腈的制备和性能研究进展

聚磷腈是一类新型无机有机复合功能高分子化合物,具有结构多样性,应用于航空航天、船舶制造、石油化工及生物医学等领域。介绍了聚磷腈的理化性质、用途、发展现状和制备方法。综述了聚磷腈的制备和性能研究进展。     

线性聚磷腈的研究进展

文章叙述了关于聚磷腈研究的国内外主要进展,讨论了磷腈取代反应的机理,归纳了各种功能高分子方面应用的线性聚磷腈的聚合方法,对未来聚磷腈功能高分子的发展方向进行了展望。     

聚磷腈的合成化学

聚磷腈是一类骨架由磷 -氮原子交替排列侧链键合各种取代基团且具有广泛应用的新型高分子化合物。本文介绍了磷腈聚合物的现状和发展 ,重点论述了聚磷腈的合成方法。     

聚磷腈的合成及其在航空领域中的研究进展

主要介绍了新型聚磷腈的合成,以及高性能聚磷腈作为阻燃材料、绝热材料、密封材料以及粘接材料等在航空领域应用的研究进展。     

聚磷腈合成的研究进展

综述了近年来聚磷腈合成的研究进展。在回顾聚磷腈的主要合成方法的基础上，介绍了出现的室温活性正离子聚合及本实验室利用卤化磷腈与五配位硅络合物反应所取得的一些结果。     

新型光学功能聚磷腈和聚硅氧烷的设计、合成和性能研究

本论文叙述两类光学功能高分子的设计、合成、结构与光学性能 .这两类高分子的主链分别是聚磷腈和聚硅氧烷 ,所研究的光学性能主要是二阶非线性光学性能 ,另外还研究了高分子的发光性能 .1　具有光学功能的聚磷腈的合成、结构与性能研究本部分合成了 1 2个新的以聚磷腈为主链的功能高分子 ,它们均经核磁共振、红外光谱、紫外 可见光谱、分子量测定等手段进行了表征 .分析了高分子的结构和组成 ,研究了高分子的发光或非线性光学性质 .1 .1　以六氯代环状磷腈三聚体单体为原料 ,在真空条件下通过开环热聚合得到聚二氯磷腈反应中间体 ,然后在四…     

聚磷腈的合成及应用研究进展

介绍了聚磷腈及中间体聚二氯磷腈的制备方法:聚磷腈由聚二氯磷腈和亲核取代试剂发生亲核反应制备;聚二氯磷腈由热开环和活性阳离子两种聚合法制备,热开环法又分为溶剂聚合、原位聚合和三氯化磷法。溶剂热开环聚合法由于获得的聚合物分子量分布较窄、分子量大和工艺条件温和等优点,适合于工业化制备。较全面地总结了聚磷腈在阻燃材料、生物医用材料、导电材料、膜材料等领域近期的研究进展和发展趋势。     

新型交联聚磷腈/聚丙烯酸羟乙酯高分子合金的制备与表征

本文首先制备了带有丙烯胺侧基的功能线性聚磷腈,通过侧基的自由基聚合,制备了交联的聚磷腈;将交联的聚磷腈置于丙烯酸羟乙酯和光引发剂的混合液中溶胀,经丙烯酸羟乙酯的光聚合反应,得到交联聚磷腈/聚丙烯酸羟乙酯高分子合金,并对其性能进行了表征。     

聚磷腈的合成和应用研究进展

聚磷腈是一类新型无机高分子,具有多种结构和有机高分子难以比拟的特性,已应用于航空航天、船舶制造、石油化工及生物医学等领域。本文介绍了聚磷腈的性质、合成方法和应用。     

HTPB-异氰酸酯体系的固化反应机理研究进展

固体推进剂和衬层配方的固化体系对其本体性能以及两者界面的黏结性能具有非常重要的影响,端羟基聚丁二烯(HTPB)和异氰酸酯是丁羟固体推进剂和衬层固化体系中最主要的组分.综述了HTPB-异氰酸酯体系的固化反应机理以及催化剂、固化剂种类和固化参数等因素对固化反应的影响.     

Issues Related with Pot Life Extension for Hydroxyl‐Terminated Polybutadiene‐Based Solid Propellant Binder System

Extension of the pot life for hydroxyl‐terminated polybutadiene (HTPB) based propellant binder systems was attempted through employing a bicurative system comprising of toluene‐di‐isocyanate (TDI) and isophorone‐di‐isocyanate (IPDI). Pot life characteristics were studied through evaluating curing kinetics for the HTPB‐bicurative binder formulations. Curing kinetics were studied through viscosity buildup during the cure reaction and estimation of the rate constants for viscosity build‐up. Introduction of IPDI slowed down the curing process, but at the same time, has not adversely affected the mechanical characteristics. One of the discouraging factors in adopting IPDI as curative is the poor interface characteristics between liner and insulator of the solid propellant grains, and it has been proposed that the root cause for the same is the permeation of IPDI through the insulator. Quantification of such permeation was attempted from the numerical values for cross‐link density evaluated for various binder compositions. Remedy for poor interface characteristics is suggested in this study.     

In–situ Characterization and Cure Kinetics in NEPE Propellant/ HTPB Liner Interface by Microscopic FT‐IR

The content distribution of chemical groups and the kinetics of curing process in the micro‐region interfaces of nitrate ester plasticized polyether (NEPE) based propellant/hydroxyl‐terminated polybutadiene (HTPB) based liner were studied by in‐situ diffuse reflection FT‐IR spectroscopy. During the curing process, the content of –NCO groups showed little increase in the liner region toward the interface. It rises quickly through the interface layer and is then stable in the region of the propellant layer, while the content of –NH groups gradually increases from liner to propellant. In the micro‐region between liner and propellant, the –C=O decreases rapidly through interface and then has a slight increase in the propellant region. Migration of nitrate esters appears at the interface of the NEPE propellant/liner at early period of curing, and –O–NO₂ decreases from propellant to liner in the bonding interface micro‐region. A study of curing kinetics indicates that the second‐order reaction model can describe the curing reaction in the bonding interface at the early stage of curing process. The order of apparent curing reaction rate constant (k ) of liner (L point), intermediate point (I point) and propellant (P point) in the interface micron‐region is k L > k I > k P at the same curing temperature. The apparent reaction activation energy (E _a) at L, I, and P points are 39.96, 81.49, and 62.51 kJ mol^–1, respectively, based on the Arrhenius equation.     

湿度对丁羟推进剂及其粘接性能的影响研究

固体火箭发动机燃烧室内绝热层、人工脱黏层及推进剂药柱，均为高分子材料复合体系。在成型及贮存过程中，湿度是影响丁羟推进剂药柱性能及各界面的联合粘接强度的首要因素。探讨了绝热层、衬层及推进剂药柱在不同环境湿度下的吸湿特性，通过模拟实际生产过程的环境湿度，研究了丁羟推进剂药柱性能及各界面的联合粘接强度变化状况。     

HTPB/IPDI推进剂与衬层界面黏结性能研究进展

简述了推进剂与衬层界面黏结机理及造成界面附近推进剂软化的原因,总结了国内外关于影响端羟基聚丁二烯(HTPB)/异佛尔酮二异氰酸酯(IPDI)推进剂与衬层界面黏结性能因素以及改善界面黏结性能的技术途径的研究成果,提出了改善该类推进剂与衬层界面黏结性能的建议.     

室温固化催化剂的研制和在固体推进剂中的应用

研制了 3种有机金属化合物TEPB p、TEPB m和TEPB o,均为白色结晶 ,纯度 >99.0 %。通过热分析方法、推进剂配方工艺研究与性能测试 ,探讨了它们对NEPE和丁羟固体推进剂固化反应的催化作用。结果表明 ,其催化活性高 ,能降低固化反应温度 ,能使推进剂药浆在室温 (35℃或 35～ 4 0℃ )保温 7～ 8d完全固化 ,并使获得的推进剂具有良好力学性能 ,因而它们可用作室温固化催化剂。     

Characterization studies on aging properties of acetyl ferrocene containing HTPB‐based elastomers

In composite solid propellants, low‐molecular‐weight species such as burning rate catalysts, plasticizer, etc. which migrate into liner and thermal insulation layers during curing and storage invariably result in poor mechanical and ballistic properties of the propellants. In the present study, the migration of the burning rate catalyst, acetyl ferrocene, was investigated spectrophotometrically (UV–visible) by evaluating the extent of hindrance to such migration after applying a barrier (liner) of various crosslink densities between the additive (HTPB‐TDI‐plasticizer–acetyl ferrocene) and nonadditive (HTPB‐TDI) gumstocks replicating the propellant and insulating layer, respectively. Enhancing the crosslink densities of liner via a trifunctional aziridine crosslinking agent inhibited migration. The aging of additive gumstock was done at 60°C and its mechanical properties and extent of acetyl ferrocene migration were also evaluated and analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2538–2545, 2006     

固化促进剂含量对HTPB–TDI衬层及其界面黏结性能影响研究

端羟基聚丁二烯–甲苯二异氰酸酯(HTPB–TDI)衬层体系配方采用固化促进剂调节衬层固化速率,通过理论分析和试验验证,研究HTPB–TDI衬层体系中不同含量固化促进剂对衬层预固化时间、本体性能、与同体系复合固体推进剂黏结性能以及老化性能的影响。结果表明,HTPB–TDI衬层配方在固化促进剂乙酰丙酮铁(ET)质量分数0.16%⁰.80%范围内进行调节,预固化时间、本体性能及老化性能满足使用要求,并与高强度复合固体推进剂的固化速度相匹配,黏结性能满足使用要求。     

特种丁羟工艺助剂的使用性能

用锥板黏度计和落球黏度计监测HTPB推进剂组分的黏度及实时固化剂TDI的消耗速度，研究了特种丁羟工艺助剂HG的组成、含量对丁羟复合固体推进剂药浆的流动性、黏度增长速度、固化特性等的影响。实验结果表明，HG能显著改进含高阻湿键合剂等丁羟预聚体配方的工艺性能，而叉保持优良的固化特性和力学性能。TDI固化剂消耗速度的监测初步证明，这些改进作用由HG干扰固化反应或所谓的类固化反应所致。     

Development of Composite Solid Propellant Based on Nitro Functionalized Hydroxyl‐Terminated Polybutadiene

This paper presents an overview of a modified composite propellant formulation to meet future requirements. The composite propellant mixtures were prepared using nitro functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) as a novel energetic binder and addition of energetic plasticizer. The new propellant formulation was characterized and tested. It was found that the Nitro‐HTPB propellant with and without energetic plasticizer exhibited high solid loading, high density, and reasonable mechanical properties over a wide range of temperatures. It was shown that the burning rate of Nitro‐HTPB propellant is up to 40% faster than that of the HTPB propellant. These results are encouraging and suggest that it should be possible to improve the ballistic performance of popular HTPB propellants through use of the studied Nitro‐HTPB binder.